Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
  • G03C1/91—Photosensitive materials characterised by the base or auxiliary layers characterised by subbing layers or subbing means
  • G03C1/93—Macromolecular substances therefor
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
  • G03C1/795—Photosensitive materials characterised by the base or auxiliary layers the base being of macromolecular substances
  • G03C1/7954—Polyesters
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S428/00—Stock material or miscellaneous articles
  • Y10S428/91—Product with molecular orientation
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/12—All metal or with adjacent metals
  • Y10T428/12229—Intermediate article [e.g., blank, etc.]
  • Y10T428/12236—Panel having nonrectangular perimeter
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31786—Of polyester [e.g., alkyd, etc.]
  • Y10T428/31797—Next to addition polymer from unsaturated monomers
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31855—Of addition polymer from unsaturated monomers
  • Y10T428/31909—Next to second addition polymer from unsaturated monomers
  • Y10T428/31928—Ester, halide or nitrile of addition polymer

Definitions

• This invention relates to synthetic film materials, and more particularly to film base materials of use in the production of photographic materials.
• self-supporting films formed of synthetic linear polyesters particularly of the polyesters formed by reaction of ethylene glycol and terephthalic acid, may be prepared with mechanical and physical and chemical properties which, for example, render them very suitable indeed as base materials on which may be coated silver halide photographic emulsion layers for the production of photographic film materials.
• film base material comprising a film of biaxially oriented synthetic linear polyester of highly hydrophobic character having superimposed thereon adherent to said film a layer which comprises a copolymer of vinylidene chloride, an alkyl acrylate or methacrylate, an allyl or methallyl component containing an active methylene group the monomer of which has the general formula ##STR2## wherein T is --CN or --COCH 3 , X is O, NH or S, and R is a hydrogen atom or methyl group and optionally at least one copolymerisable acid.
• the copolymer may comprise from 20 - 90 mole % vinylidene chloride, from 5 - 50 mole % alkyl acrylate or methacrylate, from 0 - 20 mole % copolymerisable acid and from 1 - 30% of the allyl component.
• the copolymer comprises from 40 - 85 mole % vinylidene chloride, from 10 - 40 mole % alkyl acrylate or methacrylate, from 3 - 20 mole % copolymerisable acid and from 5 - 25 mole % allyl component.
• Suitable acid units present in the copolymer are those derived from acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, mesaconic acid and citraconic acid.
• the copolymer of use in the present invention may be prepared and coated on the polyester base either as an organic solvent solution or as an aqueous latex.
• the actual copolymerisable ethylenically unsaturated monomer used in the copolymer depends on whether the copolymer is to be prepared as an organic solvent solution or as a latex.
• the alkyl acrylate or methacrylate is required to be present when the copolymer is formed because it helps to render the copolymer soluble in organic solvents and to help control the film forming properties of the copolymer.
• the preferred alkyl acrylates or methacrylates are the lower alkyl acrylates, or methacrylates i.e. those having from 1 to 4 carbon atoms in the alkyl group.
• the copolymer when the copolymer is to be prepared as an organic solvent solution preferably it comprises from 40-80 mole % vinylidene chloride, from 10-50 mole % alkyl acrylate or methacrylate, from 5-20 mole % copolymerisable acid and from 5-28 mole % of the allyl component of formula (1).
• the preferred copolymerisable acid when the copolymer is to be prepared as an organic solvent solution is acrylic acid.
• the alkyl acrylate or methacrylate is required to be present to control and modify the film - forming properties of the copolymer.
• the preferred copolymerisable acid is itaconic acid.
• the copolymer when the copolymer is to be prepared as a latex preferably it comprises from 60-85 mole % vinylidene chloride, from 7-20 mole % alkyl acrylate or methacrylate, 0.0 - 3 mole % copolymerisable acid and from 5-20 mole % of the allyl component of formula (1).
• the vinylidene chloride units give the copolymer good film-forming properties and good adhesion to the polyester.
• the presence of the allyl component of formula (1) which contains at least one active hydrogen atom in the copolymer which comprises the subbing layer enables a hydrophilic layer for example a gelatin or a polyvinyl alcohol based layer which has been coated on the film base material of the present invention to adhere very strongly to the film base material.
• the presence of the copolymerisable acid component in the copolymer helps the overall dry adhesion properties of the copolymer subbing layer.
• the allyl or methallyl cyano acetates of formula (1) may be prepared by reacting allyl or methallyl alcohol with cyanoacetic acid.
• allyl or methallyl cyanoacetamides may be prepared as described in U.S. Pat. No. 2,808,331.
• Allyl or methallyl acetoacetate may be prepared by the noncatalytic ester exchange reaction of beta-keto carboxylic acid esters as described in U.S. Pat. No. 2,693,484.
• the allyl or methallyl acetoacetamides may be prepared by the reaction of diketene with allyl or methallyl amine.
• the allyl or methallyl acetothioacetates may be prepared by reacting allyl or methallyl mercaptan with diketene.
• the allyl or methallyl cyano thioacetates may be prepared by the reaction of allyl or methallyl mercaptan with cyanoacetyl chloride.
• the preferred monomers of formula (1) for use in the copolymer of use in the present invention are those wherein R is a hydrogen atom and X is O.
• the most preferred monomer is allyl cyanoacetate.
• a particularly suitable copolymer prepared as an organic solvent solution for use in the present invention comprises 51.8 mole % vinylidene chloride, 23.0 mole % methyl acrylate, 18.3 mole % acrylic acid and 6.8 mole % allyl cyanoacetate.
• the synthetic linear polyester of highly hydropobic character which is used in the present invention must be in a layer-receptive state before the layer which comprises a copolymer of vinylidene chloride, an alkyl acrylate or methacrylate an allyl or methallyl component and optionally at least one compolymerisable acid, as hereinbefore defined, can be coated thereon.
• a polyester which has been biaxially oriented is highly hydrophobic but a film of polyester which has not been oriented at all or which been oriented in one direction only is receptive to a subbing coating. If such a subbing coating is applied to a polyester film which has been oriented in one direction only and is dried, the polyester film can then be oriented in the second direction and the applied coating as long as it comprises polymeric material which is above its second order transition temperature during the stretching will remain firmly anchored on the polyester film. This coating will then form a layer on to which more hydrophilic coatings can be applied. It is possible to coat polyester film which has not been oriented at all with a subbing layer and then to stretch it in two directions with the coating on it but this is not advantagous as the coating requires to be thicker which can lead to a poorer coating quality.
• a process for the production of film base material which comprises coating on at least one side of a film synthetic uniaxially oriented linear polyester an organic solvent solution or an aqueous latex of the copolymer as hereinbefore defined which contains units of the monomer of formula (1) drying the coating and completing the biaxial orientation.
• polyester film material and in particular biaxially oriented polyester film material may be treated so as to render its surface receptive to an applied coating.
• a process for the production of film base material which comprises treating at least one side of a film synthetic biaxially oriented linear polyester of highly hydropobic character to enable a polymer layer to adhere thereto and then coating on to the treated side or sides an organic solvent solution of the copolymer or an aqueous latex of the copolymer as hereinbefore defined which contains units of the monomer of formula (1).
• the said copolymer when the said copolymer is coated either on the uniaxially oriented or on the biaxially oriented and treated film base as an organic solvent solution the said copolymer preferably comprises from 40 - 80 mole % vinylidene chloride, from 10 - 50 mole % alkyl acrylate or methacrylate, form 5 - 20 mole % copolymerisable acid and from 5 - 25 mole % of the allyl component of formula (1).
• the copolymerisable acid is acrylic acid.
• the alkyl acrylate is methyl acrylate.
• the allyl component is allyl cyanoacetate.
• the preferred organic solvents in which to dissolve the copolymer hereinbefore defined are methyl ethyl ketone, dioxan and acetone or mixtures thereof.
• the said copolymer when the said copolymer is coated on the uniaxially oriented or the biaxially oriented and treated film base as an aqueous latex the said copolymer preferably comprises from 60 - 85 mole % vinylidene chloride, from 7 - 20 mole % alkyl acrylate or methacrylate, from 0 - 3 mole % copolymerisable acid and from 3 - 20 mole % of the allyl component of formula (1).
• the copolymerisable acid is itaconic acid.
• the alkyl acrylate is methyl acrylate.
• the allyl component is allyl acetoacetate.
• the treatment of the surface of the biaxially oriented film of synthetic linear polyester which enables a polymer layer to adhere thereto is to coat on to the surface of the polyester film an organic solvent solution or aqueous solution of a phenolic adhesion promoting agent and then to remove the solvent, preferably by evaporation.
• Synthetic organic solvents in which to dissolve the phenolic adhesion promoting agents are methanol, ethanol, methyl ethyl ketone, acetone and dioxan and mixtures thereof.
• phenolic adhesion promoting agent is meant a phenolbased or naphthol-based compound which is capable of acting on the polyester film base so as to render its surface more receptive to an applied layer.
• examples of such compounds are m - cresol, o-cresol, resorcinol, orcinol, catechol, pyrogallol, 1-naphthol each of which compounds may be substituted with one or more chloro, fluoro- or nitro substituents and phenol substituted with one or more chloro-, fluoro- or nitro-substituents.
• the action of the adhesion promoting agent on the polyester film base is thought to be swelling action and polyester surfaces so treated are receptive to certain polymeric subbing layers but not to hydrophilic layers for example a gelatin or polyvinyl alcohol.
• the film of biaxially oriented polyester may be treated by a physical method, for example corona discharge treatment, which renders the surface capable of accepting a resin layer as described in British Patent Specification Nos. 1,262,127, 1,267,215 and 1,286,457.
• the film base material of the present invention is able to accept a hydrophilic layer adherent thereto, for example a gelatin based layer, a polyvinyl alcohol layer or polyvinyl acetal layer.
• the gelatin based layer may be a gelatino silver halide emulsion layer but usually when initially biaxially oriented linear polyester film material is employed to prepare the film base material for use in the production of photographic gelatino silver halide material an intermediate gelatin layer is provided between the copolymer layer as hereinbefore defined and the silver halide emulsion layer.
• Such an intermediate layer is used in Examples 1 and 2.
• a gelatin sub layer is used between the subbing layer and the gelatino silver halide emulsion it is not necessary to have an ageing step but nevertheless the ageing step will increase the adhesion between the layers.
• hydrophilic layer to be applied to the film base material as prepared by the process of the present invention is polyvinyl alcohol or polyvinyl acetal
• a hydrophilic layer may comprise a light-sensitive diazonium salt to produce a diazotype material.
• the polyvinyl alcohol or polyvinyl acetal may have incorporated therein or be coated with a light-sensitive diazonium salt to produce a diazotype material.
• Vinylidene chloride (60.6g) was mixed together with 23.9 g of methyl acrylate, 15.9 g of acrylic acid and 10.3 g of allyl cyanoacetate in 100 ml of methyl ethyl ketone to give 50% by volume solution, the temperature of the methyl ethyl ketone being 40° C. Then as copolymerisation initiator 1.0g of 2, 2' - azobisisobutyronitrile was added to the monomer solution. The solution was maintained at 40° C until the copolymerisation was complete, which took 6 days.
• copolymer 1 Infra-red spectra and titrimetric analysis showed that substantially all the monomers had been incorporated into the copolymer which thus contained about 51.8 mole % vinylidene chloride, 23.0 mole % methyl acrylate, 18.3 mole % acrylic acid and 6.8 mole % allyl cyanoacetate. This copolymer was used in Example 1 and is referred to therein as copolymer 1.
• a second copolymer was prepared similarly using vinylidene chloride 60.6 g (50 ml), methyl acrylate 23.9 g (25 ml), acrylic acid 15.9 g (15 ml) and allyl acetoacetamide 10.4 g (10 ml).
• the resulting copolymer contained vinylidene chloride 52.2 mole %, methyl acrylate 23.2 mole %, acrylic acid 18.5 mole %, allyl acetoacetamide 6.1 mole %.
• copolymer 2 was also used in Example 1 and is referred to therein as copolymer 2.
• a third copolymer was prepared similarly using vinylidene chloride 48.5 g (40 ml), methyl acrylate 40.1 g (42 ml), acrylic acid 6.4 g (6 ml), itaconic acid 2 g and allyl acetoacetamide 10.4 g (10 ml).
• the resulting copolymer contained vinylidene chloride 43.8 mole %, methyl acrylate 40.8 mole %, acrylic acid 7.7 mole %, itaconic acid 1.3 mole % and allyl acetoacetamide 6.4 mole %.
• copolymer 3 was also used in Example 1 and is referred to therein as copolymer 3.
• a fourth copolymer was prepared similarly using vinylidene chloride 60.6 g (50 ml), methyl acrylate 23.9 g (25 ml), acrylic acid 15.9 g (15 ml) and allyl acetoacetate 10.3 g (10 ml).
• the resulting copolymer contained vinylidene chloride 52.3 mole %, methyl acrylate 23.2 mole %, acrylic acid 18.5 mole % and allyl acetoacetate 6.1 mole %.
• copolymer 4 was also used in Example 1 and is referred to therein as copolymer 4.
• a fifth copolymer was prepared similarly using vinylidene chloride 60.6 g (50 ml), methyl acrylate 23.9 g (25 ml), acrylic acid 15.9 g (15 ml) and vinyl acetate 9.3 g (10 ml).
• the resulting copolymer does not contain any allyl component of formula (1) and therefore this copolymer is not a copolymer as used in the present invention. However it was used in the comparative test set forth in Example 1 and is referred to therein as copolymer 5.
• a sixth copolymer was prepared similarly using vinylidene chloride 48.5 g (40 ml), methyl acrylate 49.7 g (52 ml), acrylic acid 6.4 g (6 ml) and itaconic acid 2 g.
• the resulting copolymer does not contain any allyl component of formula (1) and therefore this copolymer is not a copolymer as used in the present invention. However it was used in the comparative test set forth in Example 1, and is referred to therein as copolymer 6.
• the resulting particularly suitable latex comprised vinylidene chloride 84.5 mole %, methyl acrylate 8.9 mole % and allyl aceto acetate 6.7 mole %.
• Latex 1 This latex was used in Example 2 and is referred to therein as latex 1.
• a latex was prepared as in Preparation 7 but the quantities of monomers added were as follows:
• the resulting copolymer does not contain any allyl component of formula (1) and therefore this copolymer is not a copolymer as used in the present invention. However is was used in the comparative test set forth in Example 2. The latex of this preparation is designated latex 2.
• a latex was prepared as in Preparation 7 but the quantities of monomers added were as follows:
• the resulting copolymer does not comprise any allyl component of formula (1) and therefore this copolymer is not a copolymer as used in the present invention.
• the latex of this copolymer was used in the comparative test set forth in Example 2. The latex of this preparation is designated latex 3.
• the following coatings were applied sequentially to biaxially oriented film based on the synthetic linear polyester obtained from ethylene glycol and terephthalic acid which is highly hydrophobic.
• Glacial acetic acid 1.20 ml
• the following coatings were applied sequentially to three sets of samples of biaxially oriented film based on the synthetic linear polyester obtained from ethylene glycol and terephthalic acid.
• Latex 1 of preparation 7 2% solids in water together with 0.0625% of an alkyl aryl polyglycidol condensate.
• Latex 2 of preparation 8 2% solids in water together with 0.0625% of an alkyl aryl polyglycidol condensate.
• Latex 3 of preparation 9 2% solids in water together with 0.0626% of an alkyl aryl polyglycidol condensate.
• alkyl aryl polyglycidol condensate wetting agent 0.075g
• the hydrophilic layer may be an anti-halation backing layer or a photosensitive layer e.g. a silver halide emulsion layer. It is important that other layers remain firmly anchored to the base when the film material is finished, i.e. cut up into small strips and enclosed in cassettes or spooled up. Further it is important that the hydrophilic layers do not frill off when the film is placed in the camera or when removed from the camera.
• the film base of the present invention is of particular use as photographic film base in which case at least one photographic silver halide emulsion layer is coated on the subbed film base, such subbed base usually having a gelatin subcoat present between the polymer layer and the adhesion layer.
• Such photographic film material is usually processed in a sequence of aqueous processing baths and it is very important that all the final image layer is retained firmly on to the base.
• a typical processing sequence comprises immersion in the listed aqueous baths in the period stated, alkaline developer bath 3 minutes, acid stop-bath 1 minute, acid fix bath 10 minutes, aqueous washing in circulating water 20 minutes, followed by hot air drying.
• anionic surfactant 20 g
• nonionic surfactant 3 g
• Solution (a) and (b) are simultaneously pumped into a stirred 5 lite reactor under nitrogen, kept at 30° C over a period of 3 hours.
• the resulting latex was coated onto uniaxially oriented polyester prepared by extrusion onto a chilled drum, heating to between 80° and 100° C and stretching over capstan rollers of increasing circumferential speed to a draw ratio of about 3.
• the copolymer layer was dried at about 90° C and the polyester was stretched laterally in a stenter apparatus at between 80° and 100° C to a draw ratio of about 3.
• the biaxially oriented polyester was heat set at 210° C, while the tension was maintained for 1-4 minutes.
• the surface resistivity of the base was 10 9 ohms at 65% RH thus elminating the need for a further antistatic layer.
• the base was directly coated with a gelatino silver halide emulsion and after ageing at 25° C and 55% RH for 30 days, the layers showed excellent adhesion when soaked in an alkaline photographic developing solution for 10 minutes, followed by 10 minutes in an acid fix solution and water washing over 30 minutes.

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• Physics & Mathematics (AREA)
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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
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• General Physics & Mathematics (AREA)
• Laminated Bodies (AREA)
• Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
• Treatments Of Macromolecular Shaped Articles (AREA)

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• 1976
  • 1976-07-14 US US05/705,237 patent/US4098953A/en not_active Expired - Lifetime
  • 1976-07-20 CH CH928376A patent/CH622361A5/de not_active IP Right Cessation
  • 1976-07-21 DE DE19762632830 patent/DE2632830A1/de not_active Withdrawn
  • 1976-07-22 FR FR7622397A patent/FR2319144A1/fr active Granted
  • 1976-07-22 JP JP8664476A patent/JPS5213582A/ja active Pending

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